Thermoplastic polyamide polyester urethane urea resin

ABSTRACT

A thermoplastic polyamide urethane urea resin derived from (A) a liner polyhydroxyl terminated prepolymer free from ethylene terephthalate units, which has an average molecular weight of 400 to 4,000 and is liquid at 80* C., (B) a linear hydroxylterminated polyester prepolymer, which has a molecular weight of 400 to 3,000 and a melting point of 50* to 220* C. and in which 35 to 95 percent by weight of the molecular chain consists of ethylene terephthalate units, (C) a linear polyamide prepolymer having an average molecular weight of 400 to 4,000 and a melting point of 100* to 200* C., in which at least 80 percent of the both terminal groups are amino groups, and (D) an organic diisocyanate; the composition of the reaction components (A), (B), (C) and (D) being as follows: I. (D)/((A) + (B) + (C)) (mole ratio) 1 II. ((B) + (C))/(A) (weight ratio) 0.5 - 2 III. (C)/((B) + (C)) (weight ratio) 0.06 - 0.85 IV. (C)/((A) + (B) + (C) + (D)) (weight %) 3 - 55.

United States Patent 1 Tanaka et a1.

[ 51 Feb. 27, 1973 THERMOPLASTIC POLYAMIDE POLYESTER URETHANE UREA RESIN[73] Assignee: Teijin Limited, Osaka, Japan [22] Filed: April 26, 1971[21] Appl. No.: 137,657

[] Foreign Application Priority Data Apr. 28, 1972 Japan ..45/36628 [52]US. Cl. ..260/858, 117/161 KP, 161/190, 260/325, 260/ NH, 260/775 AM,

[51] Int. Cl ..C08g 41/04, C08g 22/10 [58] Field of Search...260/75 NH,77.5 AM, 77.5 SP, 260/857 PE, 858

[5 6] I References Cited UNITED STATES PATENTS 3,632,536 1/1972 lwakuraet al ..260/18 TN Primary Examiner-Donald E. Czaja Assistant Examiner-H.S. Cockeram Attorney-Sherman & Shalloway [57] ABSTRACT A thermoplasticpolyarnide urethane urea resin derived from (A) a liner polyhydroxylterminated prepolymer free from ethylene terephthalate units, which hasan average molecular weight of 400 to 4,000 and is liquid at C., (B) alinear hydroxyl-terminated polyester prepolymer, which has a molecularweight of 400 to 3,000 and a melting point of 50 to 220 C. and in which35 to percent by weight of the molecular chain consists of ethyleneterephthalate units, (C) a linear polyamide prepolymer having an averagemolecular weight of 400 to 4,000 and a melting point of to 200 C., inwhich at least 80 percent of the both terminal groups are amino groups,and (D) an organic diisocyanate; the composition of the reactioncomponents (A), (B), (C) and (D) being as follows:

i. (D)/((A) (B) (C)) (mole ratio) 1 ii. ((8) (C))/(A) (weight ratio) 0.52

iii. (C)/((B) (C)) (weight ratio) 0.06 0.85

iv. (C)/((A) (B) (C) (D)) (weight 3 10 Claims, No Drawings THERMOPLASTICPOLYAMIDE POLYESTER URETHANE UREA RESIN This invention relates to anovel thermoplastic polyamide urethane urea resin having excellentresistances to water and drycleaning, which is suitable for bonding,coating, and laminating applications, especially suitable as sewingbonding materials in such forms as films, tapes, filaments, yarns, tows,knitted and woven fabrics, and non-woven fabrics; and to a process forits production.

It is an object of the present invention to provide a novelthermoplastic polymer which has excellent properties as a bonding agentwhich is capable of meltbonding fibers or assemblies of fibers withinshort periods of time, or as a laminating or coating agent for thesefibers; and also a process for producing such a polymer.

The bonding, laminating, or coating agents for fibers or assemblies offibers are generally required to have softness, water resistance, andresistance to drycleaning. When fibers or fiber assemblies are heatmeltbonded by using a thermoplastic polyurethane, the softness is good,but generally high melting temperatures are required. There is also thedefect of poor resistance to drycleaning.

A thermoplastic polyurethane obtained by the reaction of a polyhydroxylprepolymer with a polyester prepolymer and a diisocyanate exhibitsaffinity especially for polyester fiber assemblies, and has goodresistance to water. However, it has poor resistance to drycleaning.

Polyamide type bonding agents, when used for bonding fiber assemblies,give good drycleaning resistance in general, but the bonded fiberassemblies have very hard feel and poor resistance to water.

As a result of research and development works for providingthermoplastic resins free from such defects, we have now found that anovel thermoplastic polyamide urethane urea resin derived from aspecific combination of reaction components, which has not been proposedheretofore, can be provided, and this resin has excellent improvedproperties free from the abovementioned defects.

This novel resin is a linear quaternary copolymer which can be readilyshaped by the heat melting method or by using a solvent, shows affinitynot only for polyester fibers but also for blends of polyester fibersand other fibers, and has excellent properties such as softness,resistance to water, and resistance to drycleaning as bonding,laminating, and coating agents.

The novel resin can be produced by reacting the following fourcomponents (A) to (D) under the conditions (i) to (iv):

A. A linear polyhydroxyl prepolymer containing a hydroxyl group at bothterminals but being free from ethylene terephthalate chains, which hasan average molecular weight or 400 to 4,000 and is liquid at 80 C.;

B. A linear polyester prepolymer having a hydroxyl group at bothterminals which has an average molecular weight of 400 to 3,000 and amelting point of 50 to 220 C., and in which 35 to 95 percent by weightof the molecular chain is composed of ethylene terephthalate units;

C. A linear polyamide prepolymer which has an average molecular weightof 400 to 4,000 and a melting point of 100 to 200 C., and in which atleast of both end groups consist of amino groups;

and

D. an organic diisocyanate i. (D)/(A) +(B) +(C) (molar ratio) 1 (ii) (B)+(C)/(A) (weight ratio) =0.5 2

(iii) (C)/(B) c (weight ratio) 0.06 o.ss

(iv) (C)/(A)+(B)+(C)+(D) (weight %)=355 It is known to produce athermoplastic polymer by reacting a compound having an active hydrogenatom with a polyisocyanate compound, but a polymer derived from thereaction components described above has never been proposed before.

Examples of the linear polyhydroxyl prepolymer (A) above includepolyalkylene ether glycols obtained by polymerizing ethylene oxide,trimethylene oxide, tetrahydrofuran or substituted compounds thereof,such as 1,2-propylene oxide; polyether glycols obtained by reactingaliphatic dicarboxylic acids such as succinic acid, glutaric acid,adipic acid, suberic acid, azelaic acid, or sebacic acid, or loweralcohol esters thereof (for instance, dimethyl esters), with glycols,for example, aliphatic glycols selected from ethylene glycol, 1,2-propylene glycol, trimethylene glycol, tetramethylene glycol,hexamethylene glycol, diethylene glycol, triethylene glycol, andneopentyl glycol in excess moles; polyester glycols partly containingphthalic acid, isophthalic acid, or xylene glycol; and mixtures ofthese. The preferred polyhydroxyl compounds consist mainly of aliphaticcomponents, which have an average molecular weight of 400 to 4,000,preferably 800 to 3,000 and a liquid at 80 C., preferably liquid at 60C.

The preferred linear polyester prepolymers (B) are those in which 50 topercent by weight of the molecular chain consists of ethyleneterephthalate units.

Examples of such prepolymers (B) include prepolymers derived fromterephthalic acid and/or dimethyl terephthalate and ethylene glycol.Other preferred polyester prepolymers are those consisting mainly ofaromatic components, which are obtained by condensing acid componentssuch as dicarboxylic acids, for example, isophthalic acid,Z-methylterephthalic acid, 4-methylisophthalic acid, phthalic acid,para-(beta-hydroxyethoxy)benzoic acid, 4,4- diphenyl carboxylic acid,succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid,azelaic acid, fumaric acid, maleic acid, and lower alcohol estersthereof, with glycol components such as propylene glycol, tetramethyleneglycol, hexamethylene glycol, neopentyl glycol, or diethylene glycol ofexcess moles. The prepolymers have a melting point of at least 50 C. butbelow 220 C., and an average molecular weight of 400 to 3,000.Preferably, the prepolymers have a melting point of 50C. to 200 C., andan average molecular weight of 1,000 to 2,500.

Examples of the linear polyamide prepolymers (C) are those obtained bycopolymerizing diamines with dibasic acids, derivatives thereof,omega-amino acids, or cyclic amides. The diamines are added in an excessmole over the carboxyl group so that most of the end groups of theprepolymer, preferably at least 80 percent, will be amino groups. Thediamines include, for example, aliphatic amines such as ethylenediamine, trimethylene diamine, tetramethylene diamine, pentamethylenediamine, hexamethylene diamine, heptamethylene diamine, octamethylenediamine, nonamethylene diamine, or decamethylene diamine, derivativesthereof such as 3-methoxyhexamethylene diamine; cyclic diamines such as1,3-cyclohexane diamine, 1,4-cyclohexane diamine, 1,3-hexahydroxylylenediamine, and metaxylene diamine; and diamines obtained by substitutingan ether linkage for the methylene group of said aliphatic and cyclicdiamines.

Examples of the dibasic acids that can be used include aliphaticdicarboxylic acids such as oxalic acid, succinic acid, glutaric acid,adipic acid, pimelic acid, suberic acid, azelaic acid, or sebacic acid,and lower alcohol esters thereof; and hereto atom-containingdicarboxylic acids or cyclic dicarboxylic acids such as terephthalicacid, methylterephthalic acid, hexahydroterephthalic acid, isophthalicacid, methylisophthalic acid, paraxylylenedicarboxylic acid, orisocinchomeronic acid.

Examples of the omega-aminoacids used in the invention areepsilon-aminocaproic acid, omegaaminoheptanoic acid,omega-amino-nonanoic acid, and omega-aminoundecanoic acid, and loweralcohol esters thereof.

The cyclic amides include, for example, epsiloncaprolactam orlaurolactam.

The polyamide prepolymer (C) used in the invention may also be oneobtained by partial alkylation of the nitrogen atom of the amide linkageor copolymerizing an N-alkyl polyamide. Preferably, the polyamideprepolymer (C) has a melting point of 130 to 180 C., and an averagemolecular weight of 800 to 3,500, while generally it has a melting pointof 100 C. to 200 C. and an average molecular weight of 400 to 4,000.Preferably, there are used binary to quaternary copolyamide prepolymerswhich are derived from C C lactams and/or C,,--C omega-amino acidsand/or C,,C dicarboxylic acids, and C,,C diamines, and which have anaverage molecular weight of 800 to 3,500 and a melting point of 120 to170 C., and in which at least 80% of both end groups consists of aminogroups.

The organic diisocyanates (D) that are used in the present invention arealiphatic, alicyclic, and aromatic diisocyanates, and can be expressedby the following formula OCNRNCO in which R is a residue selected fromthe group consisting of aliphatic, alicyclic, and aromatic residues.These are used either alone or in combination.

Diisocyanates of the above formula wherein R is a C,,C aliphatic residueare preferred. Examples of such siisocyanates include hexamethylenediisocyanate, dimethyl hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, metaxylylene diisocyanate, and paraxylylenediisocyanate.

Of the diisocyanates having an aromatic residue, those in which R is anaromatic residue having six to 16 carbon atoms that may be substitutedby halogen, lower alkyl, or lower alkoxy are preferred. Examples of sucharomatic diisocyanates are 2,4-tolylene diisocyanate, a mixture of2,4-tolylene by weight) and 2,6-tolylene diisocyanate (20% by weight),tetramethyl phenylene diisocyanate, diphenylmethane-4,4'-diisocyanate,metaphenylene diisocyanate, paraphenylene diisocyanate, naphthalene-l,S-diisocyanate, and diphenyl-4,4'-diisocyanate.

As the diisocyanates in which R is an alicyclic residue, those in whichthe alicyclic residue has six to 13 carbon atoms are preferred. TheExamples include isophorone diisocyanate and dicyclohexylmethanediisocyanate.

The typical method of producing the thermoplastic polyamide urethaneurea resin comprising the prepolymers (A), (B), and (C), and the organicdiisocyanate will be described specifically below.

Various methods can be used to effect this reaction. it is possible touse a method in which (C) and (D) are mixed and reacted, and then (A)and (B) are mixed and reacted. But as the reaction mixture tends to begelled at the time of mixing the components (C) and (D), it ispreferable to use other methods. For instance, the following methods canbe cited.

1. (A), (B) and (C) are mixed, and then (D) is mixed with the mixture.

2. (A) and (B) are mixed; (D) is then mixed with the mixture; and then(C) is mixed with the mixture.

3. (A) and (D) are mixed, and then the resulting mixture is mixed with amixture of(B) and (C).

4. (A) and (D) are mixed; then the resulting mixture is mixed with (B);and then (C) is mixed with the resulting mixture.

It is also possible to use a method in which one or more of thecomponents (A), (B), (C) and (D) are reacted in portions. For example,in method (4), (A) is first mixed and reacted with (D), and then theresulting mixture is mixed and reacted with a portion of (B), andfinally, a mixture of the remainder of (B) and (C) is mixed and reactedwith the resulting mixture. In any of these methods, the molar ratio of(D) to the sum of (A), (B) and (C) should be less than 1, preferably0.80 to 0.98.

According to method (1), the three prepolymers (A), (B) and (C) aremixed and heated, and the mixture is dehydrated and dried at atemperature of 80 to C. and a pressure of 2 mm Hg to 10 mm Hg;thereafter, with vigorous stirring in an atmosphere of nitrogen, theorganic diisocyanate (D) is added and reacted with the dried mixture. Atthis time, the molar ratio of (D) to the sum of (A), (B) and (C) shouldbe less than 1, preferably 0.80 to 0.98.

In method (3) in which an excess molar amount of the organicdiisocyanate (D) is reacted with the polyhydroxyl compound (A) to form alinear polyurethane prepolymer (A') having an isocyanate group at bothends, first the polyhydroxyl compound (.A) is heated, and dehydrated anddried at a temperature of 80 to 120 C. and a pressure of2 mm Hg to 10 mmHg, and then excess mole of the organic diisocyanate (D), preferably 1.52.0 moles per mole of the dihydroxyl compound (A), is added. Theresulting polyurethane prepolymer (A') having an isocyanate group atboth ends is then mixed and reacted with the prepolymers (B) and (C) inan atmosphere of nitrogen. At this time, the isocyanate equivalent ofthe polyurethane prepolymer (A) should be less than the equivalent ofthe prepolymers (B) and (C).

In any of the methods (1) to (4), the polyamide prepolymer (C) should bethose in which most, preferably at least 80 percent, of both end groupsare amino groups, the remaining carboxyl groups being less than 20percent. When the carboxyl group content is above 20 percent, sidereactions tend to occur during the reaction of the components (A) to(D). Especially when it is desired to obtain a polymer of high degree ofpolymerization containing a sufficient amount of the prepolymer (C), itis difficult to attain thermoplastic properties.

The melting points and molecular weights of the polyhydroxy] compound(A), the polyester prepolymer (B), and polyamide prepolymer (C) arechosen from the ranges specified above. The weight ratio of the sum of(B) and (C) to (A) should preferably be 0.5 to 2.0, more preferably 0.8to 1.7. The weight ratio of (C) to the sum of (B) and (C) is preferably0.06 to 0.85, more preferably 0.10 to 0.76. The weight of the polyamidecomponent in the polymer obtained by the reaction of I the prepolymers(A), (B) and (C) and the organic diisocyanate (D) is preferably 3 55percent, more preferably 5 to 45 percent.

When the weight ratio of the sum of (B) and (C) to (A) is less than 0.5,the resulting polymer has small cohesive force, large stickiness, andpoor elasticity. Where this ratio is more than 2, the resulting polymerhas an increased hardness, and the elastic properties are impaired.

When the weight ratio of (C) to the sum of (B) and (C) is smaller than0.06, the resulting polymer has poor resistance to drycleaning, and whenthis ratio exceeds 0.85, the polymer obtained has a reduced affinity forshaped articles of polyethylene terephthalate, and generally has a highsoftening point.

If the weight of the polyamide component in the resulting polymer isless than 3 percent, the polymer has a poor resistance to drycleaning,and where the weight is larger than 55 percent, the softening point ofthe polymer abruptly rises, and the elastic properties are impaired.

According to the desired properties of the thermoplastic polyamideurethane urea resin of the invention, the weight of the linear polyamideprepolymer in the resulting resin can be varied within the abovespecified range.

For example, when the weight of the polyamide component in the resultingpolymer is 3 to percent, the affinity for blends of polyethyleneterephthalate and cellulose fibers is very much improved with somedecrease of drycleaning resistance. Where the weight of the polyamidecomponent is 10 to 40 percent, both the resistance to drycleaning andthe affinity for polyethylene terephthalate articles are superior. Ifthe weight of the polyamide component is 40 to 50 percent, the affinityfor polyethylene terephthalate articles is improved to a slight degree,but the resulting polymer has good resistance to drycleaning, and goodaffinity for polyamide shaped articles.

In this way, the weight of the polyamide component in the polyamideurethane urea resin acts characteristically on the properties of theresulting resin.

The reaction of the prepolymers (A), (B) and (C) and the organicdiisocyanate (D) can be performed in the molten state. But the reactionof them in an inert solvent such as dimethyl formamide or dimethylacetamide is advantageous because it can be performed uniformly at lowertemperatures.

The thermoplastic polyamide urethane urea resin so produced can be usedwithout a curing treatment. The resin can be processed by injectionmolding, extrusion, and calendering, and used as bonding and coatingagents as already mentioned. Especially, the thermoplastic polymer ofthe invention exhibits good affinity for polyester shaped articles, forinstance, films, fibers, blends of polyester fibers and other fibers,and union cloth of polyester fibers and other fibers, and is suitable asbonding agents, coating agents, and laminating agents for thesearticles.

According to the end uses, the thermoplastic polymer of the inventionmay contain heat stabilizers, light stabilizers, antioxidants, andplasticizers.

The average molecular weights and melting points were measured by thefollowing methods.

Linear polyhydroxy prepolymer (A) 1. Measurement of OH Value (.115K-3342-1961 About one gram of the specimen is placed in a flask, and 5ml. of a reagent (100 ml. of a mixture consisting of 20 g of aceticanhydride with pyridine) is added. The flask is immersed in a glycerinebath, and maintained at to C. for one hour. It is then cooled down toroom temperature, and shaken with the addition of 1 ml. of distilledwater. The glask is further immersed in the glycerine bath for 10minutes, heated at 95 to 100 C., and then cooled down to roomtemperature. Using a phenolphthalein as an indicator, the titration ismade with a 1% N potassium hydroxide solution (one liter of a solutionof 28.05 g of potassium hydroxide in a 9:1 mixture of benzyl alcohol andmethyl alcohol).

Separately, a blank test is carried out, and the hydroxyl value of thespecimen is calculated by the following equation.

HV= (BC) X 28.05/A +NV wherein HV hydroxyl value; A weight in grams ofthe specimen; B the amount in milliters of k N potassium hydroxidesolution used in the blank test; C the amount in milliters of k Npotassium hydroxide solution used in the first-mentioned test; NVneutralization value. 2. Measurement of the carboxyl value About 1 g ofthe specimen is placed in a flask, and 50 ml. of benzyl alcohol isadded. The mixture is heated to 70 C. to form a solution. The solutionis cooled down to room temperature, and titrated with a l 100 'Npotassium hydroxide solution (one liter of a solution of 0.561 g ofpotassium hydroxide in a 9:1 mixture of benzyl alcohol and methylalcohol.) using phenolphthalein as an indicator.

Separately, a blank test is performed, and the carboxy] value iscalculated by the following equation.

where AV carboxyl value; A the weight in grams of the specimen;

C the amount in milliliters of the 1/100 N potassium hydroxide solutionin the first-described test;

B the amount in milliliters of the 1/100 N potassium hydroxide solution.

The molecular weight (MW) of the linear polyhydroxyl prepolymer (A) iscalculated by the following equation using the hydroxyl and carboxylvalues measured above.

MW=56.11/AV+HVX 2000 Linear polyester prepolymer (B) The hydroxyl andcarboxyl values are determined by the method described in Macromol.Chem. 26, 234 (1958), and the molecular weight is computed by using thesame equation as used in the determination of the molecular weight ofthe linear polyhydroxyl prepolymer (A).

Linear polyamide prepolymer (C) (1) Determination of NH concentration(equivalents/10g of polymer) About 1 g of the specimen is placed in aflask, and 25 g of phenol is added. The mixture is heated to 70 C. toform a solution. The solution is diluted with 12.5 g of ethyl alcoholand 12.5 g of distilled water. The diluted solution is cooled down toroom temperature. Then, A N hydrochloric acid is added dropwise totitrate the solution conductometrically. The NH, concentration isdetermined by the following equation.

NH concentration 0.5 C/A X 10 wherein A the weight of the specimen ingrams;

C the amount in milliliters of k hydrochloric acid which has been addeddropwise.

2. Determination of COOH (equivalents/lg of polymer) About one gram ofthe specimen is placed in a flask, and 50 ml. of benzyl alcohol isadded. The mixture is heated to 70 C. to form a solution. The solutionis then cooled down to room temperature, and titrated with l/ 100 Npotassium hydroxide solution (one liter of a solution of 0.561 g ofpotassium hydroxide in a 9:1 mixture of benzyl-alcohol and methylalcohol), using phenolphthalein as an indicator.

Separately, a blank test is performed, and the COOH concentration iscomputed by the following equation.

COOH concentration (C- B) X 0.0l/A X 10 wherein A the weight in grams ofthe specimen;

B the amount of 1/100 N potassium hydroxide solution in the blank test;and

C the amount of H100 N potassium hydroxide solution in thefirst-mentioned test.

The molecular weight (MW) of the linear polyamide prepolymer (C) iscomputed by the following equation using the NH: and COOH concentrationsobtained above.

concentration Melting point The melting points of these prepolymers aredetermined by raising the measuring temperature at a rate of 3 C/min.using a micro melting point apparatus.

The invention will be specifically illustrated by the followingExamples.

The bonding described in the Examples was performed by heat bonding for15 seconds at a pressure of 140 g/cm using a T.S.S. scorch tester. Themeasurement of the strength, and elongation of the film and themeasurement of the peel strength were performed under the followingconditions.

Specimen length 20 mm Pulling speed 40 mm/min.

Example 1 Polyethylene adipate (A) having an average molecular weight of1016 (50.8 g) was heated to 100 C., and dehydrated and dried for 30minutes at a reduced pressure of 3 mm Hg. The dried product was thenmaintained at 100 C. in an atmosphere of nitrogen. Xylylene diisocyanate(D) (meta/para=/20) (18.8 g) was added and with stirring, reacted withthe prepolymer (A) at C. for 60 minutes. The resulting polymer was apolyurethane prepolymer derived from the polyethylene adipate (A) andthe xylylene diisocyanate (D).

Separately, 51 g of a polyester prepolymer (B) having an averagemolecular weight of 1,700 composed of terephthalic acid (70)/isophthalicacid (25 )/adipic acid (5)/ethylene glycol and 30 g of a polyamideprepolymer (C) having an average molecular weight of 1,250 composed ofepsilon-aminocaproic acid (30)/nylon 66 salt (35)/nylon 6,10 salt (35)were dissolved in 100 g of anhydrous dimethyl acetamide by heating in anatmosphere of nitrogen. As a catalyst, 0.2 g of dibutyl tin dilauratewas added. With vigorous stirring at C., the polyurethane prepolymerobtained above was added, and reacted for 60 minutes at 130 C. In thisExample, the weight ratio of the components (B) and (C) to the component(A) was 1.59, and the polyamide component accounted for 20 percent byweight of the resulting polyamide urethane urea resin.

Films were prepared from a solution of the resulting resin in dimethylacetamide, and the strength and elongation of the films were measured.The film was interposed between polyethylene terephthalate fabrics wovenfrom a blend of polyethylene terephthalate fibers and cotton, and heatbonded at C. for 15 minutes. The peel strength of the film was measured.Furthermore, the heat bonded fabric was immersed for 2 hours in water orperchloroethylene, and the peel strength was measured in a wetcondition. The results are shown below.

Thickness of the film 150 microns Bread strength of the film 4.8 kg/cmBreak elongation of the film 600 Peel strength ofpolyethylene/terephthalate (65 )/cotton (35) fabrics 4.0 kglcm Peelstrength of polyethylene terephthalate knits 3.5 kg/cm Peel strength ofpolyethylene terephthalate knits immersed in water for 2 hours 3.0 kg/cmPeel strength of polyethylene terephthalate knits immersed inperchloroethylene for 2 hours 2.0 kglcm and methanol began to distilloff at about 150 C. The

temperature was raised to 210 C., and after about 600 g of methanolcontaining some water distilled off, the pressure was gradually reducedto distill off ethylene glycol. The reaction was stopped when 858 g ofethylene glycol distilled off. The polyester prepolymer obtained had amelting point of 172 C., an OH value of 65.3, a COOH value of 0.6, and amolecular weight of 1,700.

The linear polyamide prepolymer (C) having the compositionepsilon-aminocaproic acid (30)/nylon 6,6 (35)/nylon 6,10 (35) wasprepared in the following way.

Ninety grams of epsilon-aminocaproic acid, 105 g of nylon 6,6 salt, 105g of nylon 6,10 salt, 41 g of hexamethylene diamine, and 150 g of ionexchange water were mixed and heated in an atmosphere of nitrogen. At 90C., a homogeneous solution resulted, and at about 110 C., the waterbegan to distill off. The temperature was gradually raised, and in 60minutes from the beginning of distill off of water, the temperature roseto 195 C. The reaction was performed at this temperature for 60 minutes.When the distill off of water stopped, the pressure was graduallyreduced, and the reaction was performed for 30 minutes at 5 mm Hg. Theresulting polyamide prepolymer had a melting point of 144 C., an NHconcentration of 15.10 equivalents per g of polymer, a COOHconcentration of 0.90 equivalent per 10 g of polymer, and a molecularweight of 1,250. Resins (Comparative Examples 1 to 7) were prepared inthe same way as mentioned in Example 1 except that the proportions ofthe reaction components and the conditions (i) to (iv) were changed asindicated in the following table. The physical properties of theseresins are shown in the table along with the results of Example 1.

Com arative E 1 Ex D xarnp e (i) (D)/(A)+(B)+(C) 0.96 1.1 0.9

U (mole rati 6 0.96 0.96 0. 96 0. 96 0.90 (nr) Ig3)+(C)/(A) (wt. 1.691.59 2.3 0.4 1.3 1.3 1.8 1.4 (ii2u(t})/(B)+(C) (wt. 0. 37 0.37 0.37 0.250.00 0.05 0.95 0.04

o (iv) (C)/(A)+(B)+ 20 13.2 13

(CH (D) (weight 50 2.5 57 2.5 n ii i n r l rm s rollgno tio 4.8 l 4. 2Emu]: (FL/cm.) J 0 8 4 0 .5 4.0 2.5

ran 0 ongation oi the (00 1 10 M11113 (pflmenn. J 0 000 200 800 200 800e -)on ingtcmper- 150 l Patlum C) 100 120 200 140 210 140 ee strength(kg./cm.) 4.0 l 1.5 ofr'abrics of blends of O 1 O 1 5 cottonlpolyethylptepephthnllptgflk (65).

es s reugt g./cn1.) 3.5 1 1.4 of polyethylene tere- O 1 0 1 0 3 0 1'03'0 phthalate knits with each other. Peel strength (kg/cm.) 3.0 1.2 1.01.0 2.9 1.0 2.9

of above knits after Z-hour lmmersion in water.

Comparative Example Ex.

Peelstrength (kg .lcm.) 2.0 1.0 0.4 0.9 0.5 0.9 0.5

of above knits after 2- hour immersion in perchloroethylene.

1 Gellation occurred; film could not be formed.

Example 2 50.8 Grams of the polyethylene adipate (A) having an averagemolecular weight of 1,016, 51 g of the polyester prepolymer (B) havingan average molecular weight of 1,700, and 30 g of the polyamideprepolymer (C) having an average molecular weight of 1,250 were mixed,and heated to C., followed by dehydration and drying for 30 minutes at 3mm Hg. (All these prepolymers were the same as used in Example 1.)Anhydrous dimethyl acetamide (150 g) was added and the resulting mixturewas dissolved in it by heating in an atmosphere of nitrogen. Afteradding 0.2 g of dibutyl tin dilaurate as a catalyst, the mixture wasvigorously stirred at a temperature of C., and concurrently, 8.8 g ofxylylene diisocyanate (meta/para=80/20) was added dropwise. The reactionwas performed for 60 minutes at 130 to C.

In this Example, the weight ratio of the three prepolymers (A), (B) and(C) used, and the methods of their preparation were charged.

A dimethyl acetamide solution of the resulting polyamide urethane urearesin was formed into films, and the strength and elongation of thefilms were measured. Furthermore, the film was interposed between knits,and heat bonded at 155 C, for 15 seconds. The peel strength of the filmwas measured. The results were as follows:

Thickness of the film 155 microns Break strength of the film 4.3 kg/cmBreak elongation of the film 620 Peel strength of polyethyleneterephthalate knits bonded to each other 3.3 kg/cm Peel strength of theabove knits after 2-hour immersion in water 2.9 kglcm Peel strength ofthe above knits after 2-hour immersion in perchloroethylene 1.7 kg/cmExample 3 Polytetramethylene glycol (A) (68.5 g) having an averagemolecular weight of 1,370 was heated at 100 C. in an atmosphere ofnitrogen, and dehydrated and dried for 30 minutes at 3 mm Hg. At thesame temperature, 25 g of 4,4'-diphenylmethane diisocyanate (D) wasadded, and the reaction was performed with stirring at C. for 60 minutesto form a polyurethane prepolymer.

Separately, 66 g of the polyester prepolymer (B) (OH value 55.5,carboxyl value 0.5, melting point 174 C.) having an average molecularweight of 2000 and composed of terephthalic acid (70)/isophthalic acid(30)/ethylene glycol, which was prepared in the same way as set forth inExample 1, and 25.5 g of a polyamide prepolymer (C) having an averagemolecular weight of 1,250 same as that used in Example 1 were dissolvedin 120 g of anhydrous dimethyl acetamide by heating in an atmosphere ofnitrogen. After adding 0.2 g of dibutyl tin dilaurate as a catalyst, thepolyurethane prepolymer prepared above was added with vigorous stirringat 130 C., and the reaction was performed for 60 minutes at 130 to 140C. In this Example, the weight ratio of (B) (C)/(A) was adjusted to1.33, and the weight of the polyamide component in the polyamideurethane urea resin was 14 percent.

Films were prepared from a solution of the resulting polyamide urethaneurea resin in dimethylacetamide, land the strength and elongation of thefilms were measured. The films were interposed between knits in the sameway as set forth in Example 1, and heat bonded for 15 seconds at 150 C.The peel strength was then measured. The results were as followsThickness of the film 145 microns Break strength of the film 4.3 kg/cmBreak elongation of the film 750 Peel strength of polyethyleneterephthalate knits bonded to each other 3.5 kg/cm Peel strength of theabove knits after 2-hour immersion in water 2.8 kg/cm Peel strength ofthe above knits after 2-hour immersion in perchloroethylene 1.6 kg/cmExample 4 Polyethylene propylene adipate (EG/PG=70/30) (A) (82.5 g)having an average molecular weight of 1,650 was heated to 100 C. in anatmosphere of nitrogen, and dehydrated and dried for 30 minutes at areduced pressure of 3 mm Hg. Then, 18 g of xylylene diisocyanate(meta/para=80/20) (D) was added, and with stirring in an atmosphere ofnitrogen, the reaction was performed for 60 minutes at 100 C. to form apolyurethane pre-polymer.

Separately, 57.8 g of a polyester prepolymer (B) (OH value 65.5, COOHvalue 0.4, melting point 1700 C.) having an average molecular weight of1,700, which was prepared by the method described in Example 1, and 29.6g of a polyamide prepolymer (C) (NH concentration 9.91 equivalents/ g ofpolymer, COOH concentration 0.92 equivalent/10 g of polymer, meltingpoint 145 C.) having an average molecular weight of 1.850 which wasprepared from epsilonaminocaproic acid (30)/nylon 6,6 (35)/nylon 6,10(35) by the method described in Example 1 were dissolved in 125 g ofanhydrous dimethyl acetamide by heating in an atmosphere of nitrogen.After adding 0.2 g of dibutyl tin dilaurate as a catalyst, the mixturewas vigorously stirred at 130 C., and concurrently the polyurethaneprepolymer prepared above was added. The reaction was carried out at 130to 140 C. for 60 minutes. In this Example, the (B)+(C)/(A) weight ratiowas 1.06, and the weight of the polyamide component in the polyamideurethane urea resin was 16 percent.

Films were prepared from a solution of the resulting polyamide urethaneurea resin in dimethyl acetamide, and the strength and elongation of thefilms were measured. The film was interposed between polyethyleneterephthalate knits, and heat bonded at 145 C. for seconds. The peelstrength was measured. The results were as follows Thickness of the film150 microns Break strength of the film 4.0 kg/cm Break elongation of thefilm 1,200

Peel strength of polyethylene terephthalate Example 5 Polyethyleneadipate (A) (85.6 g) having an average molecular weight of 1,71 l washeated to 100 C. in an atmosphere of nitrogen, and dehydrated and driedfor 30 minutes at a reduced pressure of 3 mm Hg. Thereafter, 18 g ofxylylene diisocyanate (D) (meta/para=/20) was added, and the reactionwas performed at C. for 60 minutes in an atmosphere of nitrogen withstirring. A polyurethane prepolymer was obtained.

Separately, 58.5 g of a polyester prepolymer (B) (OH value 74.3, COOHvalue 0.4, melting point 170 C.) having an average molecular weight of1,500 and consisting of terephthalic acid (70)/isophthalic acid(30)/ethylene glycol (prepared by the method described in Example 1) and28.8 g of a polyamide prepolymer (C) having an average molecular weightof 2,617 and derived from epsilon-caprolactam, adipic acid, sebacicacid, and hexamethylene diamine (prepared by the method to be described)were dissolved in 127 g of anhydrous dimethyl acetamide by heating in anatmosphere of nitrogen. Thereafter, 0.2 g of dibutyl tin dilaurate wasadded, and then the above polyurethane prepolymer was added also. Thereaction was performed for 40 minutes at 130 to C. In this Example, theweight ratio (B)+(C)/(A) was 1.02, and the weight of the polyamidecomponent in the resulting polyamide urethane urea resin was 15 percent.

In the same way as in the previous Example, films were prepared from asolution of polyamide urethane urea resin, and the strength andelongation of the films were measured. The film was interposed betweenpolyethylene terephthalate fabrics, and heat bonded for 15 seconds at140 C. The peel strength was measured. The results were as followsThickness of the film microns Break strength of the film 3.9 kg/cm Breakelongation of the film 1,250 Peel strength of fabrics of blend ofpolyethylene terephthalate (65 )/cotton( 35) 4.0 kglcm Peel strength ofpolyethylene terephthalate knits bonded to each other 2.8 kg/cm Peelstrength of the above knits after 2-hour immersion in water 2.6 kg/cmPeel strength of the above knits after 2-hour immersion inperchloroethylene 1.5 kg/cm The polyamide prepolymer used in the presentExample was prepared in the following manner.

155 Grams of epsilon-caprolactam, 117 g of adipic acid, 133 g of sebacicacid, 210 g of hexamethylene diamine, and 300 g of ion exchange waterwere mixed and heated in an atmosphere of nitrogen. When the temperaturereached about 90 C., a homogeneous solution resulted. At this time, 0.01of MnCl -4H O and 0.008 g of CuCl 2H,O were added. At about 110 C.,water began to distill off. The temperature was continuously raised, andin about 60 minutes, it rose to C. The reaction was continued at thistemperature for 120 minutes. The pressure was gradually reduced, and thereaction was performed for 30 minutes at 5 mm Hg. Then, the reaction wasstopped.

13 The resulting polyamide prepolymer had a melting point of 149 C., anNH concentration of 7.02 equivalents/ g of polymer, a COOH concentrationof 0.62 equivalent/10 g of polymer, and a average molecular weight of2,617.

Example 6 A polyurethane prepolymer was prepared from tetramethyleneglycol (A) and 4,4'-diphenylmethane diisocyanate (D) in the same way asset forth in Example 3.

Separately, 77 g of a polyester prepolymer (01-1 value 61.7, COOH value0.5, melting point 170 C.) having an average molecular weight of 1,800and derived from terephthalic acid (70)/isophthalic acid (30)/ethyleneglycol, which was prepared by the method set forth in Example 1, wasdissolved in 80 g of anhydrous dimethyl acetamide by heating in anatmosphere of nitrogen, and 0.2 g of dibutyl tin dilaurate was added.The resulting solution held at 120 C. was added to the polyurethaneprepolymer obtained above and held at 100 C., and the mixture wasstirred. The reaction was performed for 10 minutes at 120 C. Thereafter,33.3 g of a polyamide prepolymer (C) (NI-1 concentration 5.10equivalents/10 g of polymer, COOH concentration 0.90 equivalent/10 g,melting point 164 C.) having an average molecularweight of 3,330 andprepared in the same way as described in Example 4 was dissolved in 55 gof anhydrous dimethyl acetamide by heating at 120 C. in an atmosphere ofnitrogen. The reaction was performed for 60 minutes at 130 C. In thisExample, the weight ratio (B)+(C)/(A) was 1.61, and the polyamidecomponent accounted for percent by weight of the resulting polyamideurethane urea resin.

- Films were prepared from a solution of the resulting polyamideurethane urea resin in dimethyl acetamide, and the strength andelongation of the films were measured. The film was interposed betweenpolyethylene terephthalate knits, and heat bonded at 150 C. for 15seconds. The peel strength was measured. The following results wereobtained.

Under quite the same conditions as set forth in Example 5, apolyurethane prepolymer was prepared from polyethylene adipate (A) andxylylene diisocyanate (D).

Separately, 29.8 g of a polyester prepolymer (B) (01-! value 65.5, COOHvalue 0.4, melting point 170 C.) having an average molecular weight of1,700, which was prepared from terephthalic acid (70)/isophthalic acid(30)/ethylene glycol by the method described in Example 1, and 91 g of apolyamide prepolymer (C) (NH concentration 8.20 equivalents/10 g ofpolymer, COOH concentration 0.45 equivalent/l0" g of polymer, meltingpoint 147 C.) which was prepared from epsilon-caprolactam. adipic acid,sebacic acid, and hexamethylene diamine by the method described inExample 5, and had an average molecular weight of 2,311 were dissolvedin 200 g of anhydrous dimethyl acetamide by heating in an atmosphere ofnitrogen. Then, 0.2 -g of dibutyl tin laurate was added as a catalyst,and with vigorous stirring at C., the polyurethane prepolymer preparedabove was added. The reaction was performed for 60 minutes at 130 to C.Then, 2 g of dicyclohexyl phthalate as a plasticizer was added. In thisExample, the weight ratio (B)+(C)/(A) was 1.40, and the weight of thepolyamide component in the resulting polyamide urethane urea resin was41 percent. Films were prepared from a solution of this resin indimethyl acetamide. The films had the following properties.

Thickness of the film 140 microns Break strength of the film 4.5 kg/cmBreak elongation of the film 500 Peel strength of polyethyleneterephthalate knits bonded to each other 2.6 kg/cm Peel strength of theabove knits after 2-hour immersion in water 2.4 kg/cm Peel strength ofthe above knits after 2-hour immersion in perchloroethylene 1.5 kg/cmPeel strength of nylon 6 fabrics bonded to each other 3.0 kg/cm The peelstrength was measured with respect to the specimen obtained byinterposing the film between the knits and heat bonding them at 150 C.for 15 seconds. The polyamide urethane urea resin which contains a largeamount of the polyamide prepolymer as in the present Example exhibited astrong affinity for shaped articles of polyamide.

Example 8 a blend of polyethylene terephthalate fibers and cotton.

Thickness of the film microns Break strength of the film 3.8 ltg/cmBreak elongation of the film 1,300 Peel strength of fabrics ofa blend ofpolyethylene terephthalate fibers (65)/c0tton (35) 5.2 kg/cm Peelstrength of polyethylene terephthalate knits bonded to each other 3.0kg/cm Peel strength of the above knits after 2-hour immersion in water2.8 kg/cm Peel strength of the above knits after 2-hour immersion inperchloroethylene 1.0 kg/cm Example 9 A polyurethane prepolymer. wasprepared from polyethylene adipate (A) and xylylene diisocyanate (D)under the same conditions as set forth in Example 5.

Separately, 56.1 g of a polyester prepolymer having an average molecularweight of 1,700 prepared from terephthalic acid (70)/isophthalic acid(25 )/adipic acid ()/ethylene glycol used in Example 1 and 29.8 g of apolyamide prepolymer (C) (NI-l concentration 10.52 equivalents per g ofpolymer, COOl-l concentration 0.91 equivalent per 10" g of polymer,melting point 156 C) having an average molecular weight of 1750, whichwas prepared from epsilon-caprolactam (60)/nylon 6,6 40) by the methoddescribed in Example l were dissolved in 125 g of anhydrous dimethylacetamide by heating in an atmosphere of nitrogen. After adding 0.2 g ofdibutyl tin dilaurate as a catalyst, the mixture was vigorously stirredat 130 C., and the polyurethane prepolymer prepared above was added. Thereaction was performed for 60 minutes at a temperature of 130 to 140C.

In this Example, the weight ratio (B)+(C)/(A) was adjusted to 1.0, andthe weight of the polyamide component in the polyamide urethane urearesin obtained was 15.7 percent.

Films were prepared form a solution of the resulting resin. The physicalproperties of the films were as follows Thickness of the film 140microns Break strength of the film 4.1 kg/cm Break elongation of thefilm 1,150 Peel strength of polyethylene terephthalate knits bonded toeach other 2.9 kg/cm Peel strength of the above knits after 2-hourimmersion in water 2.6 kg/cm Peel strength of the above knits afterZ-hour immersion in perchloroethylene 1.8 kg/cm Comparative Examples 8to 12 Comparative Examples 8 to 12 B. C. D. E. F.

Desmocol 176 180 1.2 0.8 0.2 9

Paraprene 225 190 1.8 1,4 0.8 10

Erbax 150 130 2.0 1.6 0.3 1 l Ester Resin 12 No.30 120 2.2 1.8 0.2

A. Comparative Example 8. Tradenames ofadhesives C, Bonding temperature(C.)

D. Peel strength of polyethylene terephthalate fabrics F. Peel strengthofthe above knits after 2 hour immersion (kg/cm) E. Peel strength oftheabove knits after 2-hour immersion (kg/cm) Desmocol 176 is a tradenamefor a polyurethane type adhesive produced by Bayer,; Paraprene 228 is apolyurethane type adhesive produced by Nippon Polyurethane Company;Erbax 150 is an ethylene/vinyl acetate adhesive produced by Du Pont;Ester Resin No.30 is a polyester type adhesive produced by Toyo SpinningCo., Ltd.; and CM 4000 is a copolyamide type adhesive produced by TorayIndustries, Inc.

Example 10 Polyethylene adipate (A) (67.5 g) having a average molecularweight of 1,350 was heated to 100 C., and dehydrated and dried for 30minutes at a reduced pressure of 3 mm Hg. Thereafter, the temperaturewas maintained at 100 C. in an atmosphere of nitrogen, and 18.8 g ofxylylene diisocyanate (metalpara=/20) (D) was added. The reaction wasperformed with stirring for 60 minutes at C. to form a polyurethaneprepolymer.

Separately, 66.3 g of a polyester prepolymer (B) (OH value 65.6, COOl-lvalue 0.3, melting point 64 to 68 C.) having an average molecular weightof 1,700 and prepared by the process described in Example 1 fromterephthalic acid (65 )/isophthalic acid (35)/ethylene glycol and 27.3 gof a polyamide prepolymer (C) having an average molecular weight of1,820 and prepared from epsilon-caprolactam, adipic acid, andhexamethylene diamine by the method to be described below were dissolvedin g of anhydrous dimethyl acetamide by heating in an atmosphere ofnitrogen. After adding 0.2 g of dibutyl tin dilaurate as a catalyst, thepolyurethane prepolymer prepared above was added, and the reaction wasperformed at C. for 60 minutes. In this Example, the (D)/(A)+(B)+(C)mole ratio was adjusted to 0.96, and the weight ratio (B)+(C)/(A), to1.39, and the weight of the polyamide component in the resultingpolyamide urethane resin was 15 percent.

Films were prepared from a solution of the resulting polyamide urethaneurea resin in dimethyl acetamide, and the strength and elongation of thefilms were measured. The film was interposed between knits, and heatbonded for 15 minutes at 137 C. The peel strength was then measured. Theresults were as follows:

Thickness of the film 140 microns Break strength of the film 3.9 kg/cmBreak elongation of the film 900 Peel strength of polyethyleneterephthalate knits bonded to each other 3.9 kg/cm Peel strength of theabove knits after 2-hour immersion in water 3.0 kg/cm Peel strength ofthe above knits after 2-hour immersion in perchloroethylene 1.7 kg/cmThe polyamide prepolymer used in this Example was prepared by thefollowing method.

Epsilon-caprolactam (2,160 g), 803 g of adipic acid, 902 g ofhexamethylene diamine, and 930 g of ionexchange water were mixed andheated in an atmosphere of nitrogen. At about 95 C., a homogeneoussolution resulted. At this time, 0.07 g of MnCl -4H O and 0.05 g ofCuCl,'2l-l 0 were added, and the temperature raising was continued. Atabout 110 C., water began to distill off, and the reaction mixture wasfurther heated to C. in about 120 minutes. The reaction was continued atthis temperature for 120 minutes. Then, the pressure was graduallyreduced, and the reaction was performed for 30 minutes at mm Hg, andthen the reaction was stopped.

The polyamide prepolymer (C) so obtained had a melting point of 155 C.,an NI-l concentration of 10.73 equivalents/ g of polymer, a COOHconcentration of 0.24 equivalent/10" g of polymer, and an averagemolecular weight of 1,820.

Example 11 A polyurethane prepolymer was prepared by the same methodwith that described in Example 10 from 55 g of polyethylene adipate (A)having an average molecular weight of 1,000 and 18.8 g of xylylenediisocyanate (meta/para=80/20) (D).

Separately, 68.4 g of a polyester prepolymer (B) (OH value 61.6, COOHvalue 0.6, melting point 70" 75 C.) having an average molecular weightof 1,800 and prepared from terephthalic acid (50)] isophthalic acid(50)/ethylene glycol by the method described in Example 1, and 21.8 g ofa polyamide prepolymer (C) having an average molecular weight of 1,820and used in Example 10 were dissolved in 120 g of anhydrous dimethylacetamide by heating in an atmosphere of nitrogen. After adding 0.2 g ofdibutyl tin dilaurate as a catalyst, the polyurethane prepolymerprepared above was added, and the reaction was performed for 60 minutesat 130 C. In this Example, the mole ratio (D)/(A)+(B)+ (C) wasadjustedto 0.95, and the weight ratio (B)+(C)/(A), to 1.6. The weight ofthe polyamide component in the polyamide urethane urea resin was 13.3percent.

Films were prepared from a solution of the resulting polyamide urethaneurea resin in dimethyl acetamide, and the strength and elongation of thefilms were measured. The film was interposed between knits, and heatbonded for seconds at 139 C. The peel strength was measured. The resultswere as follows:

Thickness of the film 150 microns Break strength of the film 3.5 kglcmBreak elongation of the film 600 Peel strength of polyethyleneterephthalate knits bonded to each other 3.3 kglcm Peel strength of theabove knits after 2-hour immersion in water 3.3 kglcm Peel strength ofthe above knits after 2-hour imi'nersion in perchloroethylene v 1.4kglcm Example 12 A polyurethane prepolymer was prepared in the same wayas set forth in Example 10 from 60.2 g of polybutylene adipate (A)having an average molecular weight of 1,204 and 18.8 g of xylylenediisocyanate (meta/para=80/20) (D).

Separately, 66.3 g of a polyester prepolymer (B) (OH value 65.3, COOHvalue 0.6, melting point 97- 100 C.) having an average molecular weightof 1,700 and prepared from terephthalic acid (67 )/a 60:40 mixture ofZ-methylterephthalic acid and 2- methylisophthalic acid (33)/ethyleneglycol by the method described in Example 1, and 22.6 g of a polyamideprepolymer (C) (NH concentration 12.01 equivalents/10 g of polymer, COOHconcentration 0.38 equivalent/10 g of polymer) having an averagemolecular weight of 1,615 and prepared from epsilon caprolactam, adipicacid, sebacic acid, and hexamethylene diamine by the method described inExample 5 were dissolved in g of anhydrous dimethyl acetamide by heatingin an atmosphere of nitrogen. After adding 0.2 g of dibutyl tindilaurate as a catalyst, the polyurethane prepolymer obtained above wasadded, and the reaction was performed for 60 minutes at C.

In this Example, the mole ratio (D)/(A)+(B)+(C) was adjusted to 0.97,and the weight ratio (B)+(C)/(A), to 1.48. The weight of the polyamidecomponent in the resulting polyamide urethane urea resin was 13.5percent.

Films were prepared from a solution of the resulting resin in dimethylacetamide, and the strength and elongation of the films were measured.The film was interposed between knits, and heat bonded at C. for 15seconds. The results were as follows immersion in perchloroethyleneExample 13 A polyurethane prepolymer was prepared from 54 g ofpolyethylene adipate (A) having an average molecular weight of 1,000 and25 g of 4,4-diphenylmethane diisocyanate (D) by the same method as usedin Example 10.

Separately, 57 g of a polyester prepolymer (B) (01-1 value 74.4, COOHvalue 0.4, melting point 59 64 C.) having an average molecular weight of1,500 and prepared from terephthalic acid (60)/isophthalic acid(40)/ethylene glycol by the method described in Example 1, and 20.3 g ofa polyamide prepolymer (C) having an average molecular weight of 1,692and prepared from epsilon-caprolactam, sebacic acid, and hexamethylenediamine by the method to be described below were dissolved in 120 g ofanhydrous dimethyl acetamide by heating in an atmosphere of nitrogen.After adding 0.2 g of dibutyl tin dilaurate as a catalyst, thepolyurethane performed obtained above was added, and the reaction waspreformed for 60 minutes at 130 C.

In this Example, the mole ratio (D)/(A)+(B)+(C) was adjusted to 0.96,and the weight ratio (B)+(C)/(A), to 1.43. The weight of the polyamidecomponent in the resulting polyamide urethane urea resin was 13 percent.

Films were prepared from a solution of the resulting resin in dimethylacetamide, and the strength and elongation of the films were measured.The film was interposed between knits, and heat bonded at 137 C. for 15seconds. The peel strength was measured. The results were as followsThickness of the film microns Break strength of the film 3.0 kglcm Breakelongation of the film 1,000 Peel strength of polyethylene terephthalateknits bonded to each other 3.1 kglcm Peel strength of the above knitsafter 2-hour immersion in water 3.0 kglcm Peel strength of the aboveknits after 2-hour immersion in perchloroethylene CuCl -2HB20. Themixture was stirred by heating in arm atmosphere of nitrogen. At about95 C., a homogeneous solution resulted. At about 1 10 C., water began todistill off. The heating was further continued, and the temperature roseto 195 C. in about 120 minutes. The reaction was continued at thistemperature for 120 minutes. Then, the pressure was gradually reduced,and the reaction was performed for 30 minutes at mm Hg, and then thereaction was stopped.

The polyamide prepolymer so obtained had a melting point of 144 C., anNH concentration of 11.53 equivalent/ g of polymer, a COOH concentrationof 0.29 equivalent/10 g of polymer, and an average molecular weight of1,692.

Example 14 A polyurethane prepolymer was prepared from polyethylenepropylene adipate (EG/PG=70/30) (A) having an average molecular weightof 1,650 and 18.8 g of xylylene diisocyanate by the same method asdescribed in Example 10.

Separately, 66.3 g of a polyester prepolymer (B) having an averagemolecular weight of 1,700 and prepared from terephthalic acid (65)lisophthalic acid (35)/ethylene glycol and 27 g of a polyamideprepolymer (C) having an average molecular weight of 1,800 and preparedby the method to be described from epsilon-caprolactam, laurolactam,adipic acid, and hexamethylene diamine were dissolved in 130 g ofanhydrous dimethyl acetamide by heating in an atmosphere of nitrogen.After adding 0.2 g of dibutyl tin dilaurate as a catalyst, thepolyurethane prepolymer obtained above was added, and the reaction wasperformed for 60 minutes at 135 C.

In this Example, the mole ratio (D)/(A)+(B)+(C) was adjusted to 0.96,and the weight ratio (B)+(C)/(A), to 1.13. The weight of the polyamidecomponent in the resulting polyamide urethane urea resin was 13.9percent.

Films were prepared from a solution of the polyamide urethane urea resinobtained, and the strength and elongation of the films were measured.The film was interposed between knits, and heat-bonded at 132 C. for 15seconds. The Peel strength was measured. The results were as followsThickness of the film 150 microns Break strength of the film 3.0 kg/cmBreak elongation of the film 1,200 Pecl strength of polyethyleneterephthalate knits bonded to each other 2.8 kglcm Peel strength ofthe-above knits after 2-hour immersion in water 2.8 kg/cm Peel strengthof the above knits after 2-hour immersion in perchloroethylene 1.3 kg/cmThe polyamide prepolymer (C) used in this Example was prepared by thefollowing method.

Epsilon-caprolactam (900 g), 1,050 g of omega-laurinlactam, 585 ofadipic acid, 678 g of hexamethylene diamine, and 750 g of ion exchangewater were added, followed by the addition of 0.05 g of MnCl -4H O, and0.04 g of CuCI -ZH O. The mixture was heated with stirring in anatmosphere of nitrogen. At about 1 10 C., water began to distill off.Heating was continued, and the temperature rose to 195 C. in aboutminutes. The reaction was continued at this temperature for 120 minutes.Then the pressure was gradually reduced, and the reaction was performedfor 30 minutes at 5 mm Hg, and then the reaction was stopped.

The polyamide prepolymer so obtained had a melting point of 135 C., anNH concentration of 10.81 equivalents/10 g of polymer, a COOHconcentration of 0.30 equivalent/10 g of polymer, and a molecular weightof 1,800.

Example 15 A polyurethane prepolymer was prepared from 62.5 g ofpolyethylene adipate (A) having an average molecular weight of 1,250 and22.2 g of isophorone diisocyanate (D) by the method described in Example10.

Separately, 66.3 g of a polyester prepolymer (B) having an averagemolecular weight of 1,700 and used in Example 10 and 27.3 g of apolyamide prepolymer (C) having an average molecular weight of 1,820 andused in Example 10 were dissolved in g of anhydrous dimethyl acetamideby heating in an atmosphere of nitrogen. After adding 0.2 g of dibutyltin dilaurate as a catalyst, the polyurethane prepolymer obtained abovewas added, and the reaction was performed for 60 minutes at C.

In this Example, the mole ratio (D)/(A)+(B)+(C) was adjusted to 0.96,and the weight ratio (B)+(C)/(A), to 1.50. The weight of the polyamidecomponent in the resulting polyamide urethane urea resin was 15.1percent.

Films were prepared from a solution of the resulting resin, and thestrength and elongation of the films were measured. The film wasinterposed between knits, and heat-bonded at 139 C. for 15 seconds.

The peel strength was measured, and the following results were obtained.

Thickness of the film 140 microns Break strength of the film 3.0 kglcmBreak elongation of the film 750 7: Peel strength of polyethyleneterephthalate knits bonded to each other 3.0 kg/cm Peel strength of theabove knits after 2-hour immersion in water 2.9 kg/cm Peel strength ofthe above knits after 2-hour 1.6 kg/cm immersion in perchloroethyleneExample 16 Thickness of the film microns Break strength of the film 3.5kg/cm Break elongation of the film 800 k Peel strength of polyethyleneterephthalate knits bonded to each other 3.5 kglcm Peel strength of theabove knits after 2-hour immersion in water 3.3 kglcm Peel strength ofthe above knits after 2-hour immersion in perchloroethylene 1.7 kg/emExample 17 Thickness or the film 150 microns Break strength of the film3.8 kg/cm Break elongation of the film 750 Peel strength of polyethyleneterephthalate knits bonded to each other 3.6 kg/cm Peel strength of theabove knits after 2-hour immersion in water 3.5 kg/cm Peel strength ofthe above knits after Z-hour immersion in perchloroethylene 1.7 kg/cmExample 18 The procedure of Example was followed except that 16.8 g ofhexamethylene diisocyanate was used instead of 22.2 g of isophoronediisocyanate. Films were prepared from a solution of the resultingpolyamide urethane urea resin, and the strength and elongation weremeasured. The film was interposed between knits, and heat-bonded at 138C. for 15 seconds. The peel strength was measured. The results were asfollows Thickness of the film 150 microns Break strength of the film 3.6kglcm Break elongation of the film 850 Peel strength of polyethyleneterephthalate knits bonded to each other 3.7 kglcm Peel strength of theabove knits after 2-hour immersion in water 3.5 kg/cm Peel strength ofthe above knits after 2-hour immersion in perchloroethylene 1.5 kglcmWhat we claim is 1. A thermoplastic polyamide urethane urea resin whichis the reaction product of A. a linear polyhydroxyl prepolymer having ahydroxyl group at both terminals and being free from ethyleneterephthalate chains, said linear poly-hydroxyl prepolymer having anaverage molecular weight of 400 to 4,000 and is liquid at 80C.,

B. a linear polyester prepolymer having a hydroxyl group at bothterminals, said linear polyester prepolymer having a molecular weight of400 to 3,000 and a melting point of 50 to 220 C. and 35 to 95 by weightof the molecular chain of said linear polyester prepolymer consisting ofethylene terephthalate units,

C. a linear polyamide prepolymer having an average molecular weight of400 to 4,000 and a melting point of 100 to 200 C., at least of the ter-65 minal groups of said linear polyamide prepolymer being amino groups,and D. an organic diisocyanate;

the composition of the reaction components (A), (B), (C) and (D) beingas follows:

i. (D)/(A) (B) (C) (mole ratio) 1 ii. (B) (C)/(A) (weight ratio) 0.5 2

iii. (C)/(B) (C) (weight ratio) =0.06 0.85

iv. (C)/(A) (B) (C) (D) (weight 3 55.

2. A thermoplastic polyamide urethane urea resin which is the reactionproduct of A. a linear polyhydroxyl prepolymer having a hydroxyl groupat both terminals and being free from ethylene terephthalate chains,said linear polyhydroxyl prepolymer having an average molecular weightof 800 to 3,000 and is liquid at 60 D.,

B. a linear polyester prepolymer having a hydroxyl group at bothterminals, said linear polyester prepolymer having an average molecularweight of 1,000 to 2,500 and a melting point of 50 to 200 C., 35 to byweight of the molecular chain of said linear polyester prepolymerconsisting of ethylene terephthalate units,

C. a linear polyamide prepolymer having an average molecular weight of800 to 3,500 and a melting point of to C., at least 80 percent of theterminal groups of said linear polyamide prepolymer being amino groups,and

D. an organic diisocyanate; the composition of the reaction components(A), (B), (C) and (D) being as follows:

i. (D)/(A) (B) (C)(mole ratio) 1 ii. (B) (C)/(A) (weight ratio) 0.5 2

iii. (C)/(B) (C) (weight ratio) =0.06 0.85

iv. (C)/(A) (B) (C) (D) (weight 3 55.

3. The thermoplastic polyamide urethane urea resin of claim 2 whereinthe composition of the reaction components (A), (B), (C) and (D) is asfollows:

i. (D)/(A) (B) (C) (mole ratio) 0.8 0.98

ii. (B) (C)/(A)(weight ratio) =0.8 1.7

iii. (C)/(B) c (weight ratio)=0.l -0.76

iv. (C)/(A) (B) (C)+ (D) (weight 5 45.

4. A thermoplastic polyamide urethane urea resin which is the reactionproduct of A. a linear aliphatic polyhydroxyl prepolymer having ahydroxyl group at both terminals and being free from ethyleneterephthalate chains, said linear aliphatic polyhydroxyl prepolymerhaving an average molecular weight of 400 to 4,000 and is liquid at atemperature of 60 C. or below,

B. a linear polyester prepolymer having a hydroxyl group at bothterminals, said linear polyester prepolymer having an average molecularweight of 1,000 to 3,000 and a melting point of 50 to 100 C., 35 percentby weight to less than 70 by weight of the molecular chain of saidlinear polyester prepolymer consisting of ethylene terephthalate units,

C. a linear polyamide prepolymer which has an average molecular weightof 400 to 4,000 and a melting point of 100 to 180 C., at least 80percent of the terminals groups of said linear polyamide prepolymerbeing amino groups,

and

D. an organic diisocyanate;

the composition of the reaction components (A), (B), (C) and (D) beingas follows:

which is the reaction product of A. a linear aliphatic polyhydroxylprepolymer having a hydroxyl prepolymer at both terminals and being freefrom ethylene terephthalate chains, said linear aliphatic polyhydroxylprepolymer having an average molecular weight of 800 to 3,000 and isliquid at a temperature of 50 C. or below,

B. a linear polyester prepolymer having a hydroxyl group at bothterminals, said linear polyester prepolymer having an average molecularweight of 1,000 to 2,500 and a melting point of 55 to 100 C., 50 percentby weight to less than 70 by weight of the molecular chain of saidlinear polyester prepolymer consisting of ethylene terephthalate units,

C. a linear polyamide prepolymer having an average molecular weight of800 to 3,500 and a melting point of 120 to 170 C., at least 80 percentof the 7. A thermoplastic polyamide urethane urea which is the reactionproduct of A. a linear polyhydroxyl prepolymer having a hydroxyl groupat both terminals and being free from ethylene terephthalate chains,said linear polyhydroxyl prepolymer having an average molecular weightof 400 to 4,000 and is liquid at 80 C. or below,

B. a linear polyester prepolymer having a hydroxyl group at bothterminals, said linear polyester prepolymer having an average molecularweight of 400 to 3,000 and a melting point of about 100 but not higherthan 200 C., a major portion of the molecular chain of said linearpolyester prepolymer consisting of ethylene terephthalate units,

C. a linear polyamide prepolymer which has an average molecular weightof 400 to 4,000 and a melting point of 100 to 200 C., at least 80percent of the terminal groups of said linear polyamide prepolymer beingamino groups,

and

D. an organic diisocyanate;

terminal groups of said linear polyamide 25 prepolymer being aminogroups, and D. an organic diisocyanate; the composition of the reactioncomponents (A), (B), (C) and (D) being as follows:

the composition of the reaction components (A), (B), (C) and (D) beingas follows:

i. (D)/(A) (B) +(C) (mole ratio) 1 ii. (B) (C)/(A) (weight ratio) =0.52.0

iii. (C)/(B) (C) (weight ratio) 0.06 0.85

i. (D)/(A) +(B) +(C) (mole ratio)=0.80-0.98

ii. (B)+ (C)/(A) (weight ratio)= 1.0- 1.8

iii. (C)/(B) (C) (weight ratio) =0.20 0.40

iv. (C)/(A)+(B)+(C)+(D)(weight%)=l025. 6. A thermoplastic polyamideurethane urea resin liquid at a temperature of 50 C. or below,

B. a linear polyester prepolymer having a hydroxyl group at bothterminals, said linear polyester prepolymer having an average molecularweight of which is the reaction product of A. a linear aliphaticpolyester prepolymer having a hydroxyl group at both terminals, andbeing free which is the reaction product of from ethylene terephthalatechains said linear A. a linear aliphatic polyhydroxyl prepolymer havingaliphatic polyester prepolymer having an average a hydroxyl group atboth terminals and being free molecular weight of 400 to 4,000 and isliquid at from ethylene terephthalate chains, said linear 80C. or below,

aliphatic polyhydroxyl prepolymer having an B. a linear polyesterprepolymer having a hydroxyl average molecular weight of 800m 2,500 andis group at both terminals, said linear polyester prepolymer having anaverage molecular weight of 400 to 3,000 and a melting point of above100 C. but not higher than 220 C. 70 to 95 percent by weight of themolecular chain of said linear 1,300 to 2,300 and a melting point of 55to 85 C. polyester prepolymer consisting of ethylene by weight to lessthan by weight of the terephthalate units,

molecular chain of said linear polyester C. a linear polyamideprepolymer which has an prepolymer consisting of ethylene terephthalateaverage molecular weight of 400 to 4,000 and a units, melting point ofto 200 C., at least 80 per- C. a linear binary to quaternary copolyamide50 cent of the terminal groups of said linear polyaprepolymer which hasan average molecular mide prepolymer being amino groups,

weight of 800 to 3,500 and a melting point of and to C. at least 80percent of the terminal D. an organic diisocyanate;

groups of said linear binary to quaternary copolya- 55 the compositionof the reaction components (A), (B),

mide prepolymer being amino groups, said prepolymer being prepared fromat least two components selected from a C,,C, lactam, a C -C omega-aminoacid, a C,,-C dicarboxylic acid and a C -C diamine,

(C) and (D) being as follows:

i. (D)/(A) (B) (C) (mole ratio) 0.80 0.98 ii. (B) (C)/(A) (weight ratio)=0.8 1.7

iii. (D)/(B) (C) (weight ratio) 0.10 0.76

iv. (C)/(A) +(B) +(C) +(D) (weight =5 -45.

and 60 9. The thermoplastic polyamide urethane urea resin (D) an organicdiisocyanate; of claim 8 which is the reaction product of thecomposition of the reaction components (A), (B), A. a linear aliphaticpolyester prepolymer having a (C) and (D) being as follows: hydroxylgroup at both terminals and being free i. (D)/(A) (B) (C) (mole ratio)0.80 0.98 65 from ethylene terephthalate chains, said linear ii. (B)(C)/(A) (weight ratio) 1.2- 1.8 iii. (C)/(B) (C) (weight ratio) =0.25-0.35 iv. (C)/(A)+(B)+(C)+(D) (weight%)=l2-20.

aliphatic polyester prepolymer having an average molecular weight of 800to 3,000 and is liquid at 60 C. or less,

B. a linear polyester prepolymer having a hydroxyl prepolymer beingamino groups,

group at both terminals, said linear polyester and prepolymer having anaverage molecular weight of D. an organic diisocyanate. 1,000 to 2,500and a melting Point of 1300 10. The thermoplastic polyamide urethaneurea resin C., 70 to 95 percent by weight of the molecular u of claim 9wherein said linear polyamide prepolymer is chain of said linearpolyester prepolymer consistg of ethylene terephthalate units a binaryto quaternary copolyamide prepolymer C. a linear polyamide prepolymerhaving an average prepared from at least twc.) components.) selecfedfrom a molecular weight of 800 to 3,500 and a melting C C12 lactamomega-ammo a point of 130 to 180 C., at least 80 percent of the 10 C12dicarboxylic acid, and a ir- 12 diamineterminal groups of said linearpolyamide

2. A thermoplastic polyamide urethane urea resin which is the reactionproduct of A. a linear polyhydroxyl prepolymer having a hydroxyl groupat both terminals and being free from ethylene terephthalate chains,said linear polyhydroxyl prepolymer having an average molecular weightof 800 to 3,000 and is liquid at 60* D., B. a linear polyesterprepolymer having a hydroxyl group at both terminals, said linearpolyester prepolymer having an average molecular weight of 1,000 to2,500 and a melting point of 50* to 200* C., 35 to 95% by weight of themolecular chain of said linear polyester prepolymer consisting ofethylene terephthalate units, C. a linear polyamide prepolymer having anaverage molecular weight of 800 to 3,500 and a melting point of 120* to180* C., at least 80 percent of the terminal groups of said linearpolyamide prepolymer being amino groups, and D. an organic diisocyanate;the composition of the reaction components (A), (B), (C) and (D) beingas follows: i. (D)/(A) + (B) + (C)(mole ratio) <1 ii. (B) + (C)/(A)(weight ratio) 0.5 - 2 iii. (C)/(B) + (C) (weight ratio) 0.06 - 0.85 iv.(C)/(A) + (B) + (C) + (D) (weight %) 3 -
 55. 3. The thermoplasticpolyamide urethane urea resin of claim 2 wherein the composition of thereaction components (A), (B), (C) and (D) is as follows : i. (D)/(A) +(B) + (C) (mole ratio) 0.8 - 0.98 ii. (B) + (C)/(A)(weight ratio) 0.8 -1.7 iii. (C)/(B) + (C) (weight ratio) 0.1 - 0.76 iv. (C)/(A) + (B) +(C)+ (D) (weight %) 5 -
 45. 4. A thermoplastic polyamide urethane urearesin which is the reaction product of A. a linear aliphaticpolyhydroxyl prepolymer having a hydroxyl group at both terminals andbeing free from ethylene terephthalate chains, said linear aliphaticpolyhydroxyl prepolymer having an average molecular weight of 400 to4,000 and is liquid at a temperature of 60* C. or below, B. a linearpolyester prepolymer having a hydroxyl group at both terminals, saidlinear polyester prepolymer having an average molecular weight of 1,000to 3,000 and a melting point of 50* to 100* C., 35 percent by weight toless than 70 % by weight of the molecular chain of said linear polyesterprepolymer consisting of ethylene terephthalate units, C. a linearpolyamide prepolymer which has an average molecular weight of 400 to4,000 and a melting point of 100* to 180* C., at least 80 percent of theterminals groups of said linear polyamide prepolymer being amino groups,and D. an organic diisocyanate; the composition of the reactioncomponents (A), (B), (C) and (D) being as follows: i. (D)/(A) + (B) +(C) (mole ratio) <1 ii. (B) + (C)/(A) (weight ratio) 0.5 - 2.0 iii.(C)/(B) + (C) (weight ratio) 0.15 - 0.60 iv. (C)/(A) + (B) + (C) + (D)(weight %) 7 -
 40. 5. A thermoplastic polyamide urethane urea resinwhich is the reaction product of A. a linear aliphatic polyhydroxylprepolymer having a hydroxyl prepolymer at both terminals and being freefrom ethylene terephthalate chains, said linear aliphatic polyhydroxylprepolymer having an average molecular weight of 800 to 3,000 and isliquid at a temperature of 50* C. or below, B. a linear polyesterprepolymer having a hydroxyl group at both terminals, said linearpolyester prepolymer having an average molecular weight of 1,000 to2,500 and a melting point of 55* to 100* C., 50 percent by weight toless than 70 % by weight of the molecular chain of said linear polyesterprepolymer consisting of ethylene terephthalate units, C. a linearpolyamide prepolymer having an average molecular weight of 800 to 3,500and a melting point of 120* to 170* C., at least 80 percent of theterminal groups of said linear polyamide prepolymer being amino groups,and D. an organic diisocyanate; the composition of the reactioncomponents (A), (B), (C) and (D) being as follows: i. (D)/(A) + (B) +(C) (mole ratio) 0.80 - 0.98 ii. (B) + (C)/(A) (weight ratio) 1.0 - 1.8iii. (C)/(B) + (C) (weight ratio) 0.20 - 0.40 iv. (C)/(A) + (B) + (C) +(D) (weight %) 10 -
 25. 6. A thermoplastic polyamide urethane urea resinwhich is the reaction product of A. a linear aliphatic polyhydroxylprepolymer having a hydroxyl group at both terminals and being free fromethylene terephthalate chains, said linear aliphatic polyhydroxylprepolymer having an average molecular weight of 800 to 2,500 and isliquid at a temperature of 50* C. or below, B. a linear polyesterprepolymer having a hydroxyl group at both terminals, said linearpolyester prepolymer having an average molecular weight of 1,300 to2,300 and a melting point of 55* to 85* C. 55 % by weight to less than70 % by weight of the molecular chain of said linear polyesterprepolymer consisting of ethylene terephthalate units, C. a linearbinary to quaternary copolyamide prepolymer which has an averagemolecular weight of 800 to 3,500 and a melting point of 120* to 170* C.at least 80 percent of the terminal groups of said linear binary toquaternary copolyamide prepolymer being amino groups, said prepolymerbeing prepared from at least two components selected from a C6-C12lactam, a C6-C12 omega-amino acid, a C6-C12 dicarboxylic acid and aC6-C12 diamine, and (D) an organic diisocyanate; the composition of thereaction components (A), (B), (C) and (D) being as follows: i. (D)/(A) +(B) + (C) (mole ratio) 0.80 - 0.98 ii. (B) + (C)/(A) (weight ratio)1.2 - 1.8 iii. (C)/(B) + (C) (weight ratio) 0.25 - 0.35 iv. (C)/(A) +(B) + (C) + (D) (weight %) 12 -
 20. 7. A thermoplastic polyamideurethane urea which is the reaction product of A. a linear polyhydroxylprepolymer having a hydroxyl group at both terminals and being free fromethylene terephthalate chains, said linear polyhydroxyl prepolymerhaving an average molecular weight of 400 to 4,000 and is liquid at 80*C. or below, B. a linear polyester prepolymer having a hydroxyl group atboth terminals, said linear polyester prepolymer having an averagemolecular weight of 400 to 3,000 and a melting point of about 100* butnot higher than 200* C., a major portion of the molecular chain of saidlinear polyester prepolymer consisting of ethylene terephthalate units,C. a linear polyamide prepolymer which has an average molecular weightof 400 to 4,000 and a melting point of 100* to 200* C., at least 80percent of the terminal groups of said linear polyamide prepolymer beingamino groups, and D. an organic diisocyanate; the composition of thereaction components (A), (B), (C) and (D) being as follows: i. (D)/(A) +(B) + (C) (mole ratio) < 1 ii. (B) + (C)/(A) (weight ratio) 0.5 - 2.0iii. (C)/(B) + (C) (weight ratio) 0.06 - 0.85 iv. (C)/(A) + (B) + (C) +(D) (weight %) 3 -
 55. 8. A thermoplastic polyamide urethane urea resinwhich is the reaction product of A. a linear aliphatic polyesterprepolymer having a hydroxyl group at both terminals, and being freefrom ethylene terephthalate chains said linear aliphatic polyesterprepolymer having an average molecular weight of 400 to 4,000 and isliquid at 80* C. or below, B. a linear polyester prepolymer having ahydroxyl group at both terminals, said linear polyester prepolymerhaving an average molecular weight of 400 to 3,000 and a melting pointof above 100* C. but not higher than 220* C. 70 to 95 percent by weightof the molecular chain of said linear polyester prepolymer consisting ofethylene terephthalate units, C. a linear polyamide prepolymer which hasan average molecular weight of 400 to 4,000 and a melting point of 100*to 200* C., at least 80 percent of the terminal groups of said linearpolyamide prepolymer being amino groups, and D. an organic diisocyanate;the composition of the reaction components (A), (B), (C) and (D) beingas follows: i. (D)/(A) + (B) + (C) (mole ratio) 0.80 - 0.98 ii. (B) +(C)/(A) (weight ratio) 0.8 - 1.7 iii. (D)/(B) + (C) (weight ratio)0.10 - 0.76 iv. (C)/(A) + (B) + (C) + (D) (weight %) 5 -
 45. 9. Thethermoplastic polyamide urethane urea resin of claim 8 which is thereaction product of A. a linear aliphatic polyester prepolymer having ahydroxyl group at both terminals and being free from ethyleneterephthalate chains, said linear aliphatic polyester prepolymer havingan average molecular weight of 800 to 3,000 and is liquid at 60* C. orless, B. a linear polyester prepolymer having a hydroxyl group at bothterminals, said linear polyester prepolymer having an average molecularweight of 1,000 to 2,500 and a melting point of 130* to 200* C., 70 to95 percent by weight of the molecular chain of said linear polyesterprepolymer consisting of ethylene terephthalate units, C. a linearpolyamide prepolymer having an average molecular weight of 800 to 3,500and a melting point of 130* to 180* C., at least 80 percent of theterminal groups of said linear polyamide prepolymer being amino groups,and D. an organic diisocyanate.
 10. The thermoplastic polyamide urethaneurea resin of claim 9 wherein said linear polyamide prepolymer is abinary to quaternary copolyamide prepolymer prepared from at least twocomponents selected from a C6-C12 lactam, a C6-C12 omega-amino acid, aC6-C12 dicarboxylic acid, and A C6-C12 diamine.